DE1806126C3 - Thermoplastic molding compounds - Google Patents

Description

irks iz «; Ät ^

with a content of not more than 10 judicial s.kah properties of polyethylene with high

Percent of another ^ -olefin or their ^ ^{hte are} j * ^Iso ^ 'f balanced and fulfilling

η ■ u ■ ^ao therefore does not meet the necessary requirements for tech-

Mixture -.as. , "" ._ " ^bb

,,. "".,., Niscke large vessels.

c) 3 to 40 weight percent of a Blockmisch- p _oi ypropylen high crystallinity has on the other

Polymensates (C) of ethylene and propylene _{seUs the} necessary for a large technical vessel

with a melt index of 0.01 to 50 _stiffness) but has a low impact

^ste · »5 toughness, especially at low temperatures, and

2. Molding compositions according to claim 1, thereby also not the required balanced indicates that the block copolymer (C) has physical properties. Also with polypropylene a two-component block copolymer of high crystallinity is therefore unsatisfactory as factory ethylene and propylene with an ethylene content of material for large technical vessels.

5 to 95 mole percent or a three-component 3 ° There have therefore already been numerous attempts to

Block copolymer from this mixed poly- improve the stiffness of polyethylene with high

merisat and made a maximum of 10 percent by weight of a density.

further \ -olefins or a mixture of min- According to a known method, the stiff-

at least two of these block copolymers with unity of the product by adding an inorganic

Different ethylene contents or a mixture 35 see substance such as silicon dioxide, carbon, clay

from this two-component block copolymer or calcium carbonate, as a reinforcing agent

Risat and the three-component block poly-polyethylene of high density improved. With this one

merisat is. Procedures, on the other hand, worsen the aK-r

3. Molding compositions according to claim 1, characterized in that the product has tensile strength and ductility. Further indicates that the ratio of melting 4 "increases the fragility temperature of the product, index of the block copolymer of ethylene and its impact strength is considerably reduced. and propylene (C) set to the melt index of the poly. Therefore, after such a procedure Ethylene (A) of high density or to melt - not a product with a balanced physical index of crystalline polypropylene (B) at most switch can be obtained.

Is 20: 1. 45 According to another known method

4. Molding compositions according to claim 1, characterized in that the melt index of the block keit of the product is lower than the melt index of the crystalline by mixing the polyethylene and propylene (C) of high density with crystalline polypropylene improves. In contrast, the impact strength At low-polypropylene (B) or the polyethylene of high temperature 50 ge ^r's prepared with the addition of a low density (A) is. Amount of crystalline polypropylene to the polyethylene

len considerably deteriorated. Hence one also receives

no product with the desired balanced properties after this process. Furthermore,

The well-known, by the medium and low pressure 55 by this method no practically significant weight reduction polyethylene of high density! End improvement of the stiffness and strength of has been achieved in recent times, for example, to molded product in that area in which the objects or Films are processed and the impact strength decreases considerably,
used for divorce-like purposes. Since the interrelationship between stiffness and high-density polyethylene has various advantages, 60 impact resistance can be seen from the drawing, such as light weight, good processability and good which the modulus of tensile elasticity (typical Merk-durability) has, its application times for the stiffness) depending on the Izod regions. One of the main application impact strength or strength for common polymer areas consists in the production of large container products and, in comparison, for the following for technical purposes, such as various containers for molding compositions according to the invention, conveying devices as well as storage containers, which are shown in place of the products obtained . The dashed curve of the conventional wooden, iron or other shows that you can use a product with at the same time good stiff metal vessels. For heat and high impact strength, ie with good

I 806 126

3 4

Any physical properties from which these products are thermally stable compared to conventional polymers cannot be obtained. The corresponding properties of the products from In Japanese Auslegeschrift 7345/66 fer high density polyethylene is clearly improved, without ner molding compounds, which 95 to 50 percent that a loss of impact strength or impact weight parts of an isotactic polypropylene, 5 to s strength of high density polyethylene must be taken with 50 parts by weight of a high pressure polyethylene in purchase. The impact strength is a density of less than 0.9 and a statistical rather even increased. In addition, the ethylene-propylene copolymers according to the invention have good processability in a proportion of the molding compositions, from 1 to 10 parts by weight per 100 parts by weight, that is, it contains improved melt flow properties and a total amount of the two other polymers. «· Improved continuous or discontinuous These molding compositions do indeed have a duration that is 2.5 to 3.3 times longer than that of resistance to tensile stresses over a longer period than that of polypropylene. In addition, the molding compositions of the OF INVENTION-Schlagzähigkett provide at -30 ⁰ C, however, the module is dung products with a good stiffness Oberflächenbeschaffender already at an addition of only up unit.

to 5 percent by weight of the rubbery ethylene. The drawing shows that both the propylene copolymers are reduced _{by 20 to 30 ° / G.} The molding compositions according to the Japanese interpretation according to Examples I to 4 from inventive writing 7345/66 thus have no balanced molding compositions are better than in terms of physical properties, in particular in the case of low products made of crystalline Polypropylene, from low temperature. 20 high density polyethylene, a two-component British patent 958079, is a closed compound of crystalline, polypropylene and poly known that the mechanical properties of high density ethylene bw. a two-component crystalline polypropylene can be improved by adding an ethylene mass of high-density polyethylene and len-propylene block copolymers. However, repylene was produced even if it was used. The graphic representation of high proportions of the ethylene-propylene block mix position shows that the values for the impact strength of the pure crystalline polypropylene products produced from the polymer only an insufficient increase in the pure crystalline polypropylene products are achieved at the top right, i.e. furthest away from, so that there is no reduction in the brittle zero point and well-balanced physics point can be expected at low temperature. 3 ° see properties.

The British patent is therefore also not The molding compositions according to the invention can be used in the

Molding compound with the desired balanced phy- Compare to the above in the drawing be ··

physical properties are available. Considered masses easier and cheaper to the

The object of the invention was to produce a wide variety of thermoplastic products, such as molded objects

Process molding compounds with improved properties for use or foils.

The molding compositions according to the invention are also the

The toughness of high-density polyethylene is described in Japanese Patent Publication "/ 345/66 -

stay * or even improved and the other molding compounds are clearly superior, like a comparison

better mechanical properties than polyethylene of the achievable values of stiffness and impact

with high density, such as improved stiffness, Fe- 40 toughness or strength, especially the falling body

Stability and high temperature resistance, as well as impact resistance, shows.

good processability, as shown in the flow table A, comparative values that correspond to the properties of the invention, exhibit. This object is achieved by the molding compositions according to the invention and corresponding ones of the invention. Molding compositions, in which, however, in place of the ethylene object of the invention are therefore thermoplastic propylene block copolymers a completely in see molding compounds, consisting of n-heptane-soluble statistical ethylene-propylem-

a) 50 to 95 percent by weight of a polymer (A) copolymer with an ethylene content of 53 Mdmit a melt index of 0.01 to 100 percent was used. Mixing, processing polyethylene with a density of at least processing and measurement took place in the comparison 0.94 or a random copolymer 50 book in the same way as with the invention of ethylene with a content of at most appropriate examples. Table A shows that with d <; r 10 percent by weight of a further \ -olefin or molding compositions according to the invention a significantly ver their mixture, better? Stiffness and impact strength, even at low

b) 2 to 40 percent by weight of a polymer (B) can be achieved at low temperatures. The reason with a melt index of 0.01 to 100 from strongly 55 for the excellent properties of the fiction-oriented crystalline polypropylene with a molding compound according to the invention is not entirely clear; ts seem content of at least 80 percent by weight, but that the ethylene chain of the Blockmiüchpolyme, -ei insoluble constituents in boiling n-hepta from ethylene and propylene a chemical and phvsi or a statistical mixed polymer of kaiische affinity to the polyethylene of propylene with a content of at most 10 overall has 60 high density, while the Propylenkett wientsprozent a further o-olefin, or their mixed polymers of this affinity to the mixture as well as ^crystal: NEN polypropylene and others chains

c) 3 to 40 percent by weight of a block copolymer of the random ethylene-propylene mixture merisats (C) of ethylene and propylene with a polymer having an affinity towards both the poly Melt index from 0.01 to 50. 65 high density ethylene as well as compared to that

Crystalline polypropylene can be obtained from the molding compositions of the invention. The invention

Products with a well-balanced physical inherent mass are therefore not only different here

manufacture shafts. The stiffness, strength and high- visually the macroscopic, but also in terms of

borrowed the microscopic structure from a simple one Polymer mixture and is based on a syn ^ rgistic interaction of the components. The inventive Composition has good processability, such as melt flow properties. The one made from it Product exhibits excellent rigidity and impact resistance and therefore well balanced physical properties.

Table A.

Comparative experiment 1
Comparative experiment 2

According to the invention
example 1

According to the invention
Example 2

High density
Polyethylene

(Parts by weight)

70 70

Crystalline

Polypropylene

(Parts by weight)

15th
10

15th
10

Statistical

Mixed polymer

from ethylene

and propylene

(Weight parts)

15 20

Block copolymer 15

Block copolymer 20 I;: od notched impact strength

23 ° C. j OC j 30 ^c C

4.5
4.6

10.0

11.0

2.5 2.7

6.0

7.0

2.1
2.0

4.5

4.9

Falling body blow toughness

-20 ° C

(kgm)

I _n O

1.5

7.3

7.8

Tensile module

kg /

60 55

95

76

Rockwell Hardness, R scale

39 37

60

61

As revealed by observation with an electron microscope or an optical microscope, the features of the composition according to the invention are based on the special structural unit and a special one Crystal or dispersion state. Of course, this depends somewhat on the component ratio and the mixed state of the composition according to the invention.

The polyethylene of high density that can be used in the composition according to the invention is polyethylene which has been produced by the low-pressure or medium-pressure process and has a density of at least 0.95; also random copolymers of ethylene with a content of not more than 10 percent by weight of "olefins, such as 1-butene, 4-methylpentene-1 or styrene, and a mixture of high-density polyethylene and the random copolymer of ethylene. It can be of great density polyethylene having a melt index of preferably 0.01, in particular 0.05 to 100 is used, to 20 (ASTM D1238-57T; 2160 g load; temperature 190 ⁰ C). The high density polyethylene with the various melt indexes is selected in this area, depending on the specific application :.

That as another component of the invention Crystalline polypropylene used in bulk consists, for example, of highly oriented crystalline polypropylene with a content of at least 80 percent by weight of substances insoluble in boiling n-heptane, a random copolymer made from propylene with a content of not more than 10 percent by weight a «-olefin, such as ethylene, butene-1, 4-methylpenien * l or styrene or a mixture of this crystalline polypropylene and the random copolymer of propylene. It can be crystalline Polypropylene with a visual point of preferably Οι, ΟΙ to 100, in particular 0.05 to 20, used willfi.

The Blpckmisch polymer consists of ethylene and propylene; from a mixed polymer containing monomeric ethylene and propylene as constituents, the individual monomeric units not being randomly strung together in Aen molecular chains of the polymer, but adjoining one another as blocks. In particular, the block copolymer of ethylene and propylene is an example of the case where at least two kinds of these blocks such as ethylene homopolymer blocks, propylene homopolymer blocks, random copolymer blocks of ethylene-propylene, etc. are not randomly distributed as constituents in the molecular chains. This also includes the non-statistical distribution of at least two types of statistical mixed polymer blocks with different ratios of ethylene to propylene.

A method for making such block blending polymers is by M. Z b a c k et al in Journal of American Chemical Society, 78, p. 2656 (published 1956). described. According to this method, a block copolymer of butadiene and styrene can be used using naphthalene anions as initiator under conditions at which the polymer molecular chain can continue to grow by ionic polymerization; This method can also be applied in a simple manner to the production of Oiefin block copolymers.

As block copolymerization catalysts mil Known catalysts can be used to promote the polymerization the olefins into a crystalline olefin polymer able to catalyze. Examples of typical such catalysts are organometallic compounds the elements of the 1st to III. Group of the periodic table or halogen compounds from transition metals the IV. to VIII. group of the periodic table.

For example, a block copolymer can be produced from ethylene and propylene by periodically and alternately bringing propylene and ethylene or a mixture of ethylene and propylene into contact with the polymerization catalyst. According to another method, the polymerization is carried out by adding ethylene and a mixture of ethylene and propylene, or a mixture of ethylene and propylene with propylene as the main component and a mixture of ethylene and propylene, in which ethylene is the main component, unit of the poly-

7 8

Mcrisationskatalysator periodically and alternately propylene should not exceed 20 and preferably not

brings in touch. be over 10. Furthermore, the melt index of the

In order to reduce the various types of olefin in the compound-block mixed polymer of ethylene and propylene

internal state with the stereospecific polymerizer as at least one of the melting indices of the critical

tion catalyst periodically and alternately in be 5 stallinen polypropylene or polyethylene of large

the surface of the Kalaly can be dense. The feature of the invention arises

sg '^ jrs with an inert gas, such as nitrogen or helium, especially if the melt index of the block

are freed from the olefin monomers; optionally copolymers in the composition according to the invention

the olefins from the catalyst surface can be lower than the melting index of polyethylene

also removed in vacuo and then the next io of great density and crystalline polypropylene is.

Olefin monomers over the catalyst surface ge especially when the block copolymers from

be directed. Ethylene and propylene from a mixture of little-

The simultaneous application of these two processes two types of block copolymers with different

rensweise leads to an improved effect. If there is a different ethylene content, preferably if

some mixing of the olefins accepted 15 the mixture at least two types of block mixing

may be the desired product manufacturing can be polymers with a content of at least 50 ° / ₀

put by simply adding \ -olefins periodically and ethylene and a block copolymer with a

alternately passes over the catalyst surface. Contains less than 50% ethylene, this shows

Product produced from the composition according to the invention without one of the process steps described above

to execute. * ° Excellent impact resistance and rigidity as well

The periodic and alternate introduction of balanced mechanical properties. the Olefins can be done once or any number of times. The individual components are uniform in the protechnical Interpolymerization can be continuously distributed, and the surface properties of the product or carried out discontinuously. Product are significantly improved. The erlin-

Examples of useful "block copolymers for 25 dung proper composition further has excellent

Use in the composition according to the invention are melt flow properties and improved processing

Block copolymers of ethylene and propylene with availability.

<~ 'nem content of 5 to 95, preferably 10 to um, a mass for a product with good whipping-90 Mole percent ethylene, three-component block strength and stiffness and very well balanced copolymers from this copolymers and not 30 physical properties according to the invention more than 10 percent by weight of another λ-olefin. one must achieve a mass with a volume of such as Bute: i-1. Pcntcn-1,4-M;: hylp; ntcn-10Jj-50 to 95Ge \ v; The percentage of polyethylene is large Styrene: furthermore a mixture of at least two of the density. 2 to 40 percent by weight of crystalline polyamide Block copolymers with different propylene and 3 brs 40 percent by weight of a block ethylene content as well as a mixture of the above two co-polymers of ethylene and propylene. component block copolymers and the three- In particular, the use of 50 to 90 glass component block copolymers. A block mixed weight percent polyethylene of high density, 5 to polymeric of ethylene and propylene with a 40 weight percent crystalline polypropylene and Melt index of preferably 0.01 to 50, in particular 5 to 40 percent by weight of a block copolymer Their 0.01 to 20 may be preferred in the 40 according to the invention from ethylene and propylene. Is the Mass can be used. Composition of the mass outside of this

The product made from it does not have the degree of polymerisation of the invention

according to mass, block copolymers used very well balanced physical properties

of ethylene and propylene must be at least as large as in the invention, but has only bad ones

be that the total sum of the degree of polymerization 45 use properties.

of the ethylene chains forming the block copolymer

does not differ significantly from the degree of polymerization of the amount of a conventional heat stabilizer, light

the composition of the invention to be mixed in with poly stabilizer or other various stabilizers

ethylene differs from high density, or which are added. Of course, one spiral expedient

Total sum of the degrees of polymerization of the 50 moderately known measures for Crystalline propylene blocks forming block mixed polymers prevent the deterioration of properties

Chains must not differ significantly from the polymeriza- single polymer during mixing and

tion degree of the to be added into the composition according to the invention.

different crystalline polypropylene. Before mixing together the inventive preferably the total sum of the polymerization mass, it is important that the constituents in the melted

homogenize grade of ethylene chains and the grand total of the state. The mixing must be as c

Degree of polymerization of the block copolymer are carried out in a temperature range, ir

Crystalline propylene chains that are formed do not result in optimal homogenization

can significantly depend on the degree of polymerisation of the polyether.

lens of high density and a degree of polymerisation of 60. A suitable temperature range for the Ver

the mix to be mixed into the composition according to the invention results from the highest melting point

differentiate crystalline polypropylene. of ver as part of the composition according to the invention

The ratio of the melt indices of the block mixed-turned polyethylene of high density, of the kii

polymeric aas ethylene and propylene to melt steel polypropylene and the block mixture poly index of high density polyethylene and 65 mers of ethylene and propylene up to tempera

Ratio of the melt indices of the block mixed polymer at which the composition according to the invention is zer

mers made of ethylene and propylene to which the invented and practically loses value, so votzagsvretsi

Crystalline poly- 200 to 300 ° C. to be added according to the mixture.

ίο

Mixing can be done by rolling, screw extrusion. Mixing can be done in a Banbury mixer or other known means. The mixing of high density polyethylene, crystalline polypropylene and block copolymer from ethylene ..nd propylene can either by simultaneous Bequeathing the three components or diirch prior mixing of two ingredients and then mixing the third ingredient into the two-component mixture take place.

The composition according to the invention will now be explained in more detail with reference to the following examples. All percentages in the examples are based on weight, unless otherwise stated.

Examples 1 to 4

Ethylene, to which a small amount of hydrogen gas was added, was polymerized in η-hexane for 1 hour, with a reaction mixture of titanium tetrachloride and diethylaluminum chloride as the catalyst has been used. Then the ethylene supply was interrupted, and the unconverted ethylene monomers were stripped from the product in vacuo. Then propylene became that, too contained a small amount of hydrogen gas as an admixture, supplied for 1 hour. After turning off the Propylene feed was removed unreacted monomeric propylene. Then it became a minor one again Amount of hydrogen gas-containing ethylene polymerized for 1 hour. This polymerization was repeated executed. The mixed polymer thus obtained was purified with methanolic hydrochloric acid, whereby a crystalline block copolymer of ethylene and propylene was obtained.

The intrinsic viscosity of the block copolymer was 2.5 (this value was obtained in a tetralin solution of 135 ° C and is generally referred to below as "inherent viscosity"). The melt index was 1.0, and the naui of the extraction with n ^ heptane remaining residue was 96%. The ethylene content of the copolymer was according to the infrared absorption spectrum determined in a manner known per se 45 mole percent.

The crystalline polypropylene produced under similar conditions as above had an inherent viscosity of 2.0, a melt index of 1.5 and an S residue insoluble in n-heptane upon extraction of 95%. The polyethylene had a density of 0.95, measured at 23 ° C; the melt index was 4.0. This polypropylene and polyethylene were melted together with the Blockmischpolymcren of ethylene and propylene in the respective amounts ratios at 190 ⁰ C in a Banbury mixer in a nitrogen atmosphere and kneaded. The kneaded mixture was passed through open rollers at room temperature and made into a sheet. This film was cut and granulated in a screw extrusion granulator at 230 ° C. in a nitrogen atmosphere. The granulated mass was then pressed into a test piece and molded according to the method described in ASTM D 638-61. This specimen was then

also subjected to condition control, and then physical properties measured in accordance with the ASTM specifications listed below and the mass correspondingly be evaluates: Izod impact strength, ASTM D 256-50, A

* 5 means kg cm / cm (notched), determined at 23 and -30 ° C tensile strength, ASTM D 412, unit kg / cm ² . Modulus of tensile elasticity, ASTM D 638-61T, unit kg / mm (cross head speed 0.51 cm / min.) Rockwell hardness, ASTM D 785-51, Unit R Scale.

Falling body impact strength: A Probcplatte ml of a thickness of 2 mm was for 1 hour at - 20 ⁰ C cooled and let fall a case body on the plate of a certain height, said de panel ^c: Blowing was added. In this test

was done. -I'lbody impact strength test device

t « ^r '? '· ^; μ Seisakusho used. The fi

J "'■■"' ''.! "Plate required energy wunJ i

η.

ur, where a deformation durt '> was determined according to ASTM D 648-58' • - ■ r., unit ⁰ C.

The results are shown in the following: > listed.

Poly-
ethy-
in the Composition, V ₀ Block mixing
polymer
from ethylene Table 1 0> C -30'C Fail body Φ MnHnI Hei train
strength skirt De- IClI Crystal
lines
Poly and propylene Izod- 4.0 3.8 & hlag-
strength
kg-in IVIUQUI uCr
train
elasticity Ocg / cm *) well-
hardness
(R- mingling
tempe-
rature Ver
gletchs-
afflicted 100 propylene 0 1.9 2.0 (-20-Q (kg / mm *) 250 Scale) CC) 90 0 0 Impact resistance
(kg - cm / cm) 1.7 1.5 6.5 81 260 40 65 1 80 10 0 23 "C 1.5 1.5 1.5 87 265 52 70 2 70 20th 0 5.2 1.9 1.0 92 275 58 80 3 90 30th 10 2.9 2.0 1.5 0.5 97 258 61 90 4th 70 0 30th 2.0 1.4 1.4 3.0 89 280 50 72 5 0 0 0 1.7 1.0 100 390 63 88 6th 100 4.0 6.0 4.5 0.01 118 87 116 7th 70 15th 3.0 7.0 4.9 287 example 70 15th 20th 1.5 6.0 4.2 7.3 95 288 60 91 1 80 10 IO 4.5 4.0 7.8 96 28C 61 95 2 60 10 20th 10.0 5.7 95 · 297 60 85 3 20th $ 11 6.0 f05 75 100 4th 9.0 8.5

For comparison purposes, crystalline polypropylene, high density polyethylene, its two-part composition were used made of crystalline polypropylene and high density polyethylene, which by similar Mix in the same way as the three-component mass was produced, as well as a two-component mass High density polyethylene and a copolymer of ethylene and propylene, each granulated and shaped and then the corresponding physical properties are determined in an analogous manner.

As can be seen from Table 1, the inventive Compounds according to Examples 1 to 4 products with good impact resistance, good stiffness and good strength, i.e. well balanced physical properties, compared to products that Made of high density polyethylene, crystalline polypropylene, a two-component mass of crystalline Polypropylene and high density polyethylene as well as a pure two-component mass of polyethylene of high density and a block copolymer of ethylene and propylene.

The properties of the composition according to the invention are excellent, as can also be seen from the graphic Representation results.

Examples 5 to 7

A block polymer was produced from ethylene and propylene in the same way as in Examples 1 to 4, except that the ethylene, which has a smaller admixture of hydrogen gas, was added in a different amount and a product with an inherent viscosity of 2.0, a melt index of 1.9, a residue of 96 ⁿ / r> insoluble in n-heptane and an ethylene content of 10 mol percent, determined by infrared absorption spectrum, was obtained. This produced a block copolymer of ethylene and propylene with an inherent viscosity of 3.0, a melt index

ίο of 0.5, a residue insoluble in the extraction with n-heptane of 97 ° / ₀ and an ethylene content of 80 mol percent mixed so that the mixture of block copolymers of ethylene and propylene had an ethylene content of 64 mol percent.

From the crystalline polypropylene used according to Examples 1 to 4 and the above block copolymers were three-component compositions of the composition listed in Table 2 below manufactured. These masses became test pieces in the same manner as in Examples 1 to 4 and the physical properties were tested according to ASTM regulations.

As can be seen from Table 2, the prepared according to Examples 5 to 7 according to the invention Masses have good impact resistance and stiffness and thus well-balanced physical properties on. The composition according to the invention was also particularly easy to process, and so was the molded product had a good surface finish.

Table 2

Poly- Composition, ° / " Block mixing
polyjneres Izod- OC -30 C Falling body Module of the train skirt V'erfor- ethy- from ethylene Impact resistance 6.2 4.7 Blow 1 * 1 XJXA VJ I u & I
Train-
clasticity strength well- mingling example len Crystal
lines and propylene (kg ■ cm / cm) 5.5 4.2 strength
kg η hardness tempe-
rature 80 Poly 10 7.0 5.0 (kg / mm ³ ) (kg / cm *) (R- 70 propylene 10 23 = C (-20 ⁰ C) 96 285 Scale) CC) 5 60 10 20th 11.0 8.0 99 290 62 79 6th 20th 10.5 7.5 UO 3G. ' 65 89 7th 20th 12.5 9.0 75 100

Examples 8 to 9

A block copolymer of ethylene was prepared in the same manner as in Examples 1 to 4, with the exception that a mixture of ethylene and propylene with a small amount of hydrogen gas was used in place of propylene with a small amount of hydrogen gas. A block copolymer with an inherent viscosity of 1.9, a melt index of 2.3, a residue of 82% insoluble in n-heptane during extraction and an ethyte content of 89 mol percent, determined by the infrared absorption spectrum, was obtained. Crystalline polypropylene was produced more finely in the same manner as in Examples 1 to 4, a product having a residue insoluble in the extraction with n-Hep tan of 96%, an intrinsic viscosity of 1.8 and a melt index of 3.0 was obtained. These two products were mixed with polyethylene with a density of 0.95 ur4 and a melt index of 2.0 in the proportions shown in Table 3 to give three-component compositions.

The physical properties of the obtained in the same manner as in the previous examples presented products were made in the same way as there definitely; the results obtained are ii listed in Table 3 below. From the tabefl "

SS shows that the product produced from the inventive masses according to Examples 8 and 9 «a? have excellent impact resistance and stiffness .

Table 3

Poly Composition, · / « Block mix
polymer Izod- (TC -30 C Case body Module <W train
strength skirt De- example Crystal
lines from ethylene Impact resistance
flcg cm / cm) 8.5 5.0 Impact resistant
no:
kg-m train
elasticity well-
hardness mingling
tempe-
rature Poly and propylene 6.5 4.5 (kg / cm ⁵ ) (R- 70 propylene 20th 2TC <-20 ⁵ C) (kg / cm *) 287 Skalay VCy 8th 80 10 10 14.0 7.5 96 282 65 90 9 10 9.0 7.1 93 60 77

Examples 10-11

It became a block copolymer on the same Way as in Examples 1 to 4 produced with the Exception that a mixture of ethylene and propylene with a low hydrogen content instead of the Ethylene with a low hydrogen content was used. A product with a Intrinsic viscosity of 1.9, a melt index of 2.1, a residue of 85% insoluble in the extraction with n-heptane and an ethylene content of Π mole percent determined by infrared absorption spectrum, receive. This product is made with high density polyethylene and crystalline polypropylene according to Examples 1 to 4 in the proportions listed in Table 4 to the price component masses mixed.

The physical properties of the products made from these masses have been investigated: the results obtained are shown in Table 4 below. This table shows itself.

ίο that one from the Dreillcomponentenmassen according to the invention according to Examples 10 to III products with excellent impact resistance and rigidity.

table

Poly Composition, "/ ■ Block mix
polymer Izod- OC -30 C Falling body Train-
clasticity train
fixed wedge skirt De- Betspiel If »η Crystal
lines from ethylene Impact resistance
(kg cm / cm) 3.5 3.0 Schiagfestig-
speed
kg ■ m well-
hardness mingling
tempe-
rature Poly and propylene 3.2 2.9 (kg / cm ¹ ) (kg / cm ² ! (R- 70 propylene 15th 23 C (20 O 94 287 Scale) (C) 10 60 15th 20th 5.2 4.9 97 293 66 91 11th 20th 5.0 4.5 75 101

Example 12

A three-component composition was prepared in the following proportions, with statistical Copolymers of propylene with a content of 3 mol percent ethylene and an inherent viscosity of 1.7, a melt index of 2.3 and a residue of insoluble in n-heptane during extraction 88 ° / "instead of the crystalline polypropylene according to Examples 8 to 9 and the same polyethylene from high density and the block copolymers of ethylene and propylene according to Examples 8 to 9 are used became:

High density polyethylene '.. 80%

Block copolymer 10%

Random mixed polymer of propylene 10%

The physical properties of one of the requirements of the invention The mass of the product prepared according to Example 12 were examined, the following being investigated Results obtained were:

Izod impact strength

23 ° C 10.0

0 ° C 7.5

-30 ⁰ C 5.0

Rockwell hardness 57

Modulus of tensile elasticity 93

40

D:>. The product thus obtained had both excellent Stiffness and impact strength in comparison with the products obtained according to Examples 1 to 7 and had well-balanced physical properties. The composition according to the invention also showed good melt flowability.

Example 13

A three-component composition was prepared with the composition listed below. It became the same crystalline polypropylene and oil copolymers of ethylene and propylene as used in Examples 1 to 4: instead of high density polyethylene, however, a statistical one was used Copolymer of ethylene with a content of 2 mol percent propylene, a melt index of 6.0 and a density of 0.94, determined at 23'C. used. The mixing ratios are as follows listed:

Random mixed polymer of ethylene 70%

Block copolymer 20%

crystalline polypropylene 10%

The physical properties of a product made from this composition were determined, where the following results were obtained:

Izod impact strength

23 ° C 6.2

0 ° C 3.7

-30'C 3.1

Rockwell hardness 65

Modulus of tensile elasticity 95

The product made from the above composition thus had good impact resistance and rigidity as well improved breaking strength under load.

Example 14

Propylene with a low hydrogen content was polymerized for 30 minutes, using as a catalyst a reaction mixture of titanium tetrachloride and diethyl aluminum chloride was used. To turning off the propylene feed were not reacted Stripped propylene monomers from the product in vacuo. Then butene-1 was with a initiated low hydrogen content for 5 minutes and then unreacted 1-butene im Vacuum removed. Ethylene with a low hydrogen content was then fed in for 1 hour. Then monomeric propylene with a low hydrogen content was fed again after previously unreacted ethylene had been removed. The polymerization was carried out repeating this Proceedings continued. The mixed poly-

I 806

mere was purified with methanolic hydrochloric acid, a powdery crystalline three-component block mixed polymer was obtained from ethylene, propylene and butene.

The mixed polymer thus obtained had an inherent viscosity of 2.8, a melt index of 0.8 and a residue of 94% remaining after the extraction with n-heptane. From the infrared absorption spectrum of the copolymer resulted in a content of 72 mol percent ethylene, 23 mol percent Propylene and 5 mole percent butane.

It was a three-component composition in the following mixing ratio of crystalline polypropylene with an inherent viscosity of 1.5, a melt index of 8.0 and one when extracted with n-heptane insoluble residue of 95%. Polyethylene with a density of 0.96 and a melt index of 1.2 as well as the above three-component block copolymer:

High density polyethylene 70%

crystalline polypropylene 10%

Three-component

Block copolymer 20%

The physical properties of one "wJ mass hefgestellten product urtOTWoht were wuirden contact the following results:

Izod impact strength

Rockweli hardness J *

Modulus of tensile elasticity ^ll "

From the mass produced according to this example, a product with good rigidity and good Establish impact resistance. The above composition also had good melt-moldability upon molding became a product with a good surface finish receive.

Example 16

A mixture in a weight ratio of 1: 1 of the crystalline used according to Examples 1 to 4 d d

Polypropylene and the random copolymer of propylene with a content of 3 mol percent Ethylene was used as crystalline polypropylene. A mixture in a weight ratio of 1: 1 according to

The physical properties of one of these 25 «- ■ ·· v .. ^ .... ^.,.". ". _. ·,

Mass-produced products were investigated, where Examples 1 to 4 used polyethylene mn

high density and the random copolymer of ethylene with a content of 2 mole percent propylene Example 13 was used as the high density polyethylene. The three-component block copolymer of ethylene, propylene and butene according to Example 14 was used as the block copolymer. , From the above polyethylene blend of high

From the mass produced according to this example 35 density, the crystalline ™ *? ^το ™ ¹ * ^η & ™ * \ "! Ζ can therefore be a product with good impact resistance and the three-component block copolymer

⁵ 6 6 .. _{a three-component mass} , in the following mix

relationship established:

High density polyethylene 60%

crystalline polypropylene mixture 20 / "

Three-component

Block copolymer 20 / "

G
where the following results were obtained:

Izod impact strength

23 ° C 12.0

0 ⁰ C 7.8

-30 ⁰ C 4.9

Rockwell hardness 55

Modulus of tensile elasticity 91

♦ °

Establish rigidity as well as excellent processability.

Example 15

It was a three-component mass in the following mixing ratios from a mixture in a weight ratio of 1: 1 of a block copolymer of ethylene and propylene with a - _r ..j

Ethylene content of 45 mol% according to the product manufactured in the two 45 masses was investigated, wospiel 1 to 4 and a block copolymer from which the following results were obtained: Ethylene and propylene with an ethylene content of 89 mol percent according to Examples 8 to 9, the statistical Copolymers of propylene with a content of 3 mol percent ethylene according to Example 12 50 and the high density polyethylene produced according to Examples 8 to 9:

The physical properties of a product made from this material were investigated.

Izod impact strength

23 ° C

0 ^J C

-30'C

Rockweli hardness

7.0 5.0 4.2 67

High density polyethylene 70%

Block copolymer mixture 20%

Random copolymer of propylene 10%

Tensile elasticity module 99

The mass produced in accordance with this example thus resulted in a product with good rigidity and good rigidity Impact resistance obtained. The mass had good processability.

1 sheet of drawings

Claims (1)

the durability of such vessels, it is imperative that the polymer used is one of-1, Thermoplastic molding compounds, consisting of sufficient rigidity and impact strength, in particular a) 50 to 95 percent by weight of a Polymerisa- a high impact strength at low temperature, tes (A) with a melt index of 0.01 to ⁵ has. The physical properties of this 100 made of polyethylene with a density of polymers used must therefore well balanced mindestensO, 94odereinemstatistischen mixing ^{se 'n} ·.
polymer has of ethylene having a content of high density polyethylene, although a maximum of 10 weight percent of a WEI excellent impact strength at low Tempe Teren "olefin, or a mixture thereof ^{l0 temperature} · However, ^{it has} several serious disadvantages b) 2 to 40 percent by weight of a Polymerisa- * j ™ ± ^ if / A ^ ^ ΪΕ. " and the